EP1331033A1 - Kügelförmige hochaktive Metall-Trägerkatalysatoren - Google Patents
Kügelförmige hochaktive Metall-Trägerkatalysatoren Download PDFInfo
- Publication number
- EP1331033A1 EP1331033A1 EP03001147A EP03001147A EP1331033A1 EP 1331033 A1 EP1331033 A1 EP 1331033A1 EP 03001147 A EP03001147 A EP 03001147A EP 03001147 A EP03001147 A EP 03001147A EP 1331033 A1 EP1331033 A1 EP 1331033A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- catalyst
- mass
- mixture
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 9
- 239000005017 polysaccharide Substances 0.000 claims abstract description 9
- 150000004676 glycans Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- -1 zirconates Chemical class 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 4
- 150000004645 aluminates Chemical class 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229940072056 alginate Drugs 0.000 claims description 9
- 235000010443 alginic acid Nutrition 0.000 claims description 9
- 229920000615 alginic acid Polymers 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052914 metal silicate Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 30
- 239000002245 particle Substances 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000725 suspension Substances 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract description 2
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 150000004760 silicates Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000661 sodium alginate Substances 0.000 description 5
- 235000010413 sodium alginate Nutrition 0.000 description 5
- 229940005550 sodium alginate Drugs 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000013379 physicochemical characterization Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003752 zinc compounds Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BUBXGTRYKSVANQ-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Mn+2].[Co+2] Chemical compound [O-2].[O-2].[Ti+4].[Mn+2].[Co+2] BUBXGTRYKSVANQ-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- LRLQEYKKTKXUJQ-UHFFFAOYSA-N cobalt(2+) manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Mn+2].[Co+2].[Ti+4].[O-2].[O-2].[O-2] LRLQEYKKTKXUJQ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XQCUWCZUYXJXRL-UHFFFAOYSA-N copper dioxosilane Chemical compound [Si](=O)=O.[Cu] XQCUWCZUYXJXRL-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
- B01J2/08—Gelation of a colloidal solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- B01J35/51—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B01J35/392—
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- B01J35/393—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
Definitions
- the invention relates to spherical supported metal catalysts, a process for their manufacture and a process for the hydrogenation of Aromatics.
- US 2001/0012816 A1 describes the dropletization of mixtures of polysaccharide solutions with hydrated Al 2 O 3 , SiO 2 Al 2 O 3 , ZrO 2 Al 2 O 3 or TiO 2 Al 2 O 3 gels or with Al 2 O 3 -, B 2 O 3 Al 2 O 3 - or B 2 O 3 SiO 2 Al 2 O 3 hydrates in an aqueous solution of Ca 2+ -, Al 3+ -, Mg 2+ -, Ba 2+ - or Sr 2+ ions.
- Another method of making spherical Catalyst is the granulation process, however does not lead to uniform ball sizes. Further disadvantages of this method are the rough one Surface of the balls as well as the uneven distribution the pore sizes over the spherical cross-section.
- Spherical catalysts can also be used made by "spheronizers". in this connection are previously made moldings on a rotating Plate deformed into balls, as in the example of oxide carriers described in WQ 99/58236 becomes. In this process, the porosity to a great extent when deformed into extrudates predetermined and the uniformity of the ball size and spherical shape is also unsatisfactory.
- the present invention is therefore technical Underlying problem, highly active metal supported catalysts to provide for hydrogenation processes, which have a uniform ball size and ball shape as well as high metal dispersity, high Porosity and an even distribution of Have pore sizes.
- the present invention is also technical Underlying problem, manufacturing process to provide such catalysts.
- This technical problem is solved according to the invention in that a method for the production of shaped spherical metal supported catalysts with metal contents of 10 to 70 mass% is provided, whereby a mixture of at least one polysaccharide and at least one iron, dissolved or suspended in a liquid medium, Cobalt, nickel, copper or zinc compound from the group of metal oxides, metal hydroxides, basic metal carbonates, metal hydrogen carbonates, metal silicates, metal zirconates, metal aluminates, metal titanates, metal chromites or metal aluminosilicates is dripped into a metal salt solution, the metal ions of which are preferably also components of the at least one selected Are metal compound.
- metal salt solution Compounds of other polyvalent cations, such as Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Al 3+ and Cr 3+ , are preferably used as metal salt solution according to the invention.
- the spherical catalyst moldings obtained from the mixture in this metal salt solution are separated from the mixture after a residence time of 1 to 180 minutes, dried at temperatures from 80 to 150 ° C. and reduced at temperatures from 150 to 600 ° C.
- the shaped catalyst articles are then preferably stabilized in a manner known per se.
- the inventive method makes spherical Get catalyst moldings, the one have a very uniform spherical shape.
- the one with the Catalysts obtained by the process according to the invention also have a highly uniform particle size on.
- catalysts obtained by the process according to the invention with a significantly increased pore volume significantly more macropores above 50 nm.
- the invention leads to the high proportion of macropores rapid removal of the reduction water the catalyst molding.
- a particular advantage of the The method according to the invention therefore also consists in the very high metal dispersities of the reduced Catalysts.
- Catalyst moldings also exist after the Reduction in high mechanical strength at the same time high pore volume.
- the pore structure of the obtained Catalysts according to the invention specifically adjusted become.
- Solid ratios are preferred according to the invention (based on the residue on ignition) of 4 to 15, in particular from 4.4 to 8.5.
- alginate is preferably used as the polysaccharide.
- According to the invention is preferred as a liquid Medium water used.
- the mechanical Strength of the balls by at least a solid and / or liquid aggregate that to which at least one iron, cobalt, nickel, Copper or zinc compound, preferably before Dripping, is added and as a binder acts increases.
- solid ratios are preferred (based on the residue on ignition) of at least one Iron, cobalt, nickel, copper or zinc compound to the at least one aggregate of 4 to 15, especially from 10 to 12.
- Catalysts can be set specifically.
- Mechanical strength is preferred according to the invention of the catalyst obtained by nature and concentration of the at least one metal ion in the metal salt solution, especially in a dropping column, certainly.
- iron salt solutions for supported iron catalysts preference is given to using iron salt solutions for supported iron catalysts, cobalt salt solutions for supported cobalt catalysts, nickel salt solutions for supported nickel catalysts, copper salt solutions for supported catalysts and zinc salt solutions for supported catalysts.
- the metal salt solutions can also contain other polyvalent metal ions or mixtures thereof, in particular the metals magnesium, calcium, strontium, barium, manganese, aluminum or chromium, such as Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Al 3+ or Cr 3+ .
- this is at least a metal salt in the aforementioned metal salt solution as metal nitrate and / or metal acetate in front.
- at least one metal salt in an amount of 0.3 to 5 mass%, preferably of 1 to 2% by mass in the metal salt solution.
- the metals iron, cobalt, nickel, copper and / or Zinc additionally at least one doping element from the group magnesium, calcium, manganese, molybdenum, Chromium, iron and zinc in an amount of 0.1 up to 5 mass% added, preferably 1 to 3 mass%. In a particularly preferred embodiment for doping manganese in an amount of 2% by mass used.
- the reaction is preferably carried out in the reduction and stabilizing the dried or annealed Prior art catalysts made, as well as exemplary in the exemplary embodiments explained.
- the ratio of metal compound (based on the residue on ignition) and the alginate used (solid) in the mixture is 4.4, the metal compound / aggregate ratio is 7.
- the solution is dripped into a liquid column, which is an aqueous solution of nickel nitrate (1% nickel) contains.
- the distance between the drip head and liquid surface is about 10 cm, the total solution volume is 1.5 1.
- the evenly shaped Balls settle on the bottom of the container. After more complete The material thus produced becomes droplet 30 minutes for complete curing in leave the solution.
- the dried catalyst is then in one suitable integral reactor in a nitrogen stream Temperatures of approx. 350 ° C and after conversion on hydrogen (gas pollution approx. 2000 v / vh) reduced for 6 h at temperatures of 400 ° C.
- the pyrophoric catalyst is then stabilized using an air / nitrogen mixture (starting with O 2 concentrations of 0.1% by volume to 2% by volume).
- the catalyst according to the invention obtained therefrom contains 58% nickel and has a degree of reduction of 75%.
- the nickel metal surface (determined by CO chemisorption) is 50 m 2 / g catalyst, the average nickel crystallite size is 3 nm and the bulk density is 0.5 kg / l.
- the catalyst of the invention also has one excellent uniformity of particle size distribution on: The average diameter is at 2.15 mm. All catalyst particles have one Diameters from 2.0 to 2.3 mm.
- Table 2 shows the characteristics of the mechanical and physico-chemical characterization of the catalyst produced according to the invention summarized. It can be seen from this that the obtained catalyst due to an extremely high pore volume with appealing strength distinguishes the catalyst moldings.
- the powder used has a density of approx. 0.3 kg / l and an average grain size of approx. 8 ⁇ m on.
- the ratio of metal compound (based on the residue on ignition) and the alginate used (solid) in the mixture is 7.5, the metal compound / aggregate ratio is 13.
- the suspension becomes Ultraturrax as in Example 1 described in an aqueous nickel acetate solution (5% nickel) dripped.
- the dripped material is stored 15 min in the nickel acetate solution.
- the pyrophoric catalyst is stabilized in a nitrogen / air / carbon dioxide mixture in a manner known per se.
- the CO 2 content in the gas mixture is 1% by volume.
- the catalyst according to the invention obtained contains 55% nickel and has a degree of reduction of 60%.
- the nickel metal surface (determined by means of CO chemisorption) is 33 m 2 / g of catalyst, the nickel crystallite size is 2.7 nm and the bulk density is 0.4 kg / l.
- the catalyst obtained also has an excellent one Uniformity of particle size distribution with a medium diameter from 2.6 mm. All have catalyst particles a diameter of 2.4 to 2.8 mm.
- the ratio of metal compound (based on the residue on ignition) and the alginate used (solid) in the mixture is 6, the metal compound / aggregate ratio is 12.
- Example 1 Path The preparation of the dropletizable catalyst suspension takes place on the given in Example 1 Path.
- the dropletization of the solution is in a 3% Nickel nitrate solution made.
- the dropletized catalyst particles show a very uniform Shape and size.
- the catalyst balls are made in the same way as in the example 1 conditions described.
- the catalyst according to the invention obtained contains 65% nickel and has a degree of reduction of 70%.
- the nickel metal surface (determined by means of CO chemisorption) is 28 m 2 / g catalyst, the nickel crystallite size is 3.7 nm and the bulk density is 0.75 kg / l.
- the catalyst obtained also has a good one Uniformity of particle size distribution.
- the average particle diameter is 2 mm.
- All Catalyst particles have a diameter of 1.9 to 2.2 mm.
- the ratio of metal compound (based on the residue on ignition) and the alginate used (fixed) is 8.5.
- the metal compound / surcharge ratio is 10.6.
- the preparation of the dropletizable catalyst suspension takes place on the given in Example 1 Path.
- the dropletization of the catalyst slurry is in made a 1.5% calcium nitrate solution.
- the dripped particles have a uniform shape and round shape.
- the catalyst of the invention is before catalytic assessment for the hydrogenation of substituted aromatics at temperatures of 400 ° C reduced and stabilized in a conventional manner.
- All catalyst particles have a diameter of 1.8 up to 2.2 mm.
- the ratio of metal compound (based on residue on ignition) and used alginate (solid) in the mixture is 12.25, the metal compound / aggregate ratio is 4.
- the catalyst of the invention obtained has an average particle size of 2 mm and records themselves through a uniform size and shape out.
- the catalyst is reduced in a nitrogen / hydrogen stream (2% H 2 ) at temperatures of 200 ° C. and then stabilized according to example 1.
- the finished catalyst contains 65% copper and has a degree of reduction of 70%.
- the middle Copper primary particle size is 8.7 nm.
- the catalyst of the invention also has one good uniformity of particle size distribution on. All catalyst particles have one Diameters from 1.8 to 2.1 mm, the average particle diameter is 1.9 mm and the bulk density is 0.4 kg / l.
- Dried and ground nickel / SiO 2 starting material with an average grain size of 10 ⁇ m and a bulk density of 0.7 kg / l is mixed with tylose as a binder and then peptized in a laboratory kneader with the addition of condensate water, nitric acid and silica sol solution.
- the addition of tylose is 2.5% based on the solids content of the kneading batch. After a kneading time of 15 minutes, the complete batch is formed into 3 mm full strands in a laboratory extrusion press with a cutting device.
- the moist extrudates obtained are then further processed into spheres in a laboratory spheronizer (Caleva, Model 120, England).
- the spherical material obtained is then dried at 130 ° C. and has the grain spectrum shown in Table 1.
- the Catalyst particles In addition to the very broad grain spectrum, the Catalyst particles a non-uniform and Part of irregular spherical shape.
- the catalyst material obtained is then reduced at 400 ° C in a hydrogen stream and below Standard conditions stabilized in a manner known per se.
- the comparative catalyst obtained contains 55% nickel and has a degree of reduction of 75%.
- the nickel metal surface (determined by CO chemisorption) is 30 m 2 / g catalyst, the average nickel crystallite size is 4.5 nm and the bulk density is 0.8 kg / l.
- the catalyst shows a broad particle size distribution with diameters from 2 to 4 mm.
- Example 4 Cobalt-manganese-titanium dioxide catalyst starting material becomes 3 mm x 3 mm with the addition of graphite Tablets deformed. Following the deformation the catalyst material is as described in Example 4 reduced and stabilized.
- the finished catalyst has a bulk density of 1.2 kg / l and a compressive strength of 35 MPa.
- the copper-silica catalyst raw material used in Example 5 is calcined at 350 ° C and then with the addition of tylose, Condensate and nitric acid in a suitable Mixing unit peptized and then closed 1.6 mm Trilobe extrudates deformed. After drying and calcination of the moldings takes place the reduction and stabilization of the starting material among the conditions described in Example 5.
- the finished catalyst contains 70% copper and has a degree of reduction of 75%.
- the bulk density is 0.85 kg / l, the copper crystallite size at 9.2 nm.
- a commercially available spherical nickel-aluminosilicate catalyst with the following physico-chemical characteristics is also used for the catalytic assessment: Nickel content (mass%) 55 Degree of nickel reduction (%) 60 Bulk density (kg / l) 0.95 Average particle diameter (mm) 2.5 Particle diameter range (mm) 1.6 to 4.7 Nickel crystallite size (nm) 5.1
- this catalyst has a very non-uniform spherical shape. In addition to spherical particles of different sizes, it also contains extrudates and extrudate fragments.
- Physico-chemical and mechanical characteristics of the catalysts produced according to the invention and of the comparison catalysts catalyst Bulk density (kg / l) abrasion (%) Total pore volume (cm 3 ) Pore volume> 50 nm (cm 3 / g) 1 (inventive) 0.5 0.8 0.84 0.52 2 (inventive) 0.4 1.0 0.95 0.64 3 (inventive) 0.75 0.7 0.60 0.29 4 (inventive) 0.5 0.3 0.45 0.29 5 (inventive) 0.4 1.2 0.82 0.58 6 (compare) 0.8 0.55 0.30 0.02 7 (compare) 1.2 0.5 0.27 0.14 8 (compare) 0.85 1.2 0.30 0.07 9 (compare) 0.95 0.8 0.35 0.04
- the built-in catalyst volume is 50 ml.
- the 50 ml catalyst volume are each in 10 Servings with 10 servings of SiC in Volume ratio of 1: 1 installed.
- the catalysts are reactivated in a hydrogen stream (50 l / h) over a period of 4 h at 250 ° C.
- a kerosene with an aromatic content of 18% by mass and a sulfur content of 1.1 ppm is used as feed.
- the reaction conditions are: reaction pressure 30 bar reaction temperature 85 ° C 100 ° C reaction time 40 h 80 h LHSV 1.3 ml / ml ⁇ h Gas-product volume ratio H 2 / kerosene 400: 1
- the cobalt-manganese-titanium dioxide catalyst (example 4) is used in the hydrogenation of isocamphylpyrocatechol catalytic to sandal alcohols tested.
- a comparative catalyst is a pill Catalyst (Example 7) of the same composition tested.
- the catalytic test is carried out in a fixed bed process using an integral flow reactor (inner diameter: 25 mm). It becomes a catalyst volume of 50 ml.
- the 50 ml catalyst volume comes in 10 servings with 10 servings each SiC installed in a volume ratio of 1: 1.
- the catalysts are reactivated in a hydrogen stream (50 l / h) over a period of 3 h at 300 ° C.
- a mixture of isocamphylpyrocatechol and cyclohexanol (1: 1) is used as feed.
- the other reaction conditions are: reaction pressure 70 bar reaction temperature 220 ° C reaction time 50 h LHSV (isocamphyl pyrocatechol) 0.5 ml / ml ⁇ h.
- Example 5 With the same reactor system as in Example 11, the catalytic characterization of the copper-silicon dioxide catalyst (Example 5) is carried out in the acetophenone hydrogenation.
- the catalyst from Example 8 serves as a comparative catalyst.
- a mixture of 70% by mass acetophenone and 30% by mass methyl-phenyl-carbinol is used as feed.
- the other reaction conditions are: reaction pressure 20 bar reaction temperature 80 ° C reaction time 40 h LHSV 0.5 ml / ml ⁇ h Gas-product volume ratio H 2 / feed 250: 1
Abstract
Description
Korngröße (mm) | Masse-% |
> 5 | - |
4-5 | 0,1 |
3-4 | 10,7 |
2,5-3,0 | 39,9 |
2,0-2,5 | 25,8 |
1,6-2,0 | 16,1 |
1,0-1,6 | 7,4 |
< 1,0 | - |
Nickelgehalt (Masse-%) | 55 |
Nickelreduktionsgrad (%) | 60 |
Schüttdichte (kg/l) | 0,95 |
Mittlerer Partikeldurchmesser (mm) | 2,5 |
Partikeldurchmesserbereich (mm) | 1,6-4,7 |
Nickelkristallitgröße (nm) | 5,1 |
Physikalisch-chemische und mechanische Kenndaten der erfindungsgemäß hergestellten Katalysatoren und der Vergleichskatalysatoren | ||||
Katalysator | Schütt-dichte (kg/l) | Abrieb (%) | Gesamtporen-volumen (cm3) | Poren-volumen >50 nm (cm3/g) |
1 (erfind.) | 0,5 | 0,8 | 0,84 | 0,52 |
2 (erfind.) | 0,4 | 1,0 | 0,95 | 0,64 |
3 (erfind.) | 0,75 | 0,7 | 0,60 | 0,29 |
4 (erfind.) | 0,5 | 0,3 | 0,45 | 0,29 |
5 (erfind.) | 0,4 | 1,2 | 0,82 | 0,58 |
6 (Vergl.) | 0,8 | 0,55 | 0,30 | 0,02 |
7 (Vergl.) | 1,2 | 0,5 | 0,27 | 0,14 |
8 (Vergl.) | 0,85 | 1,2 | 0,30 | 0,07 |
9 (Vergl.) | 0,95 | 0,8 | 0,35 | 0,04 |
Reaktionsdruck | 30 bar | |
Reaktionstemperatur | 85°C | 100°C |
Reaktionszeit | 40 h | 80 h |
LHSV | 1,3 ml/ml·h | |
Gas-Produkt-Volumenverhältnis H2 / Kerosin | 400:1 |
Katalysator | Reaktionstemperatur 85 °C | Reaktionstemperatur 100°C |
Aromaten-Anteil im Reaktionsprodukt (ppm) | Aromaten-Anteil im Reaktionsprodukt (ppm) | |
1 (erfind.) | 1600 | 150 |
2 (erfind.) | 1750 | 160 |
3 (erfind.) | 1550 | 152 |
6 (Vergl.) | 2640 | 259 |
9 (Vergl.) | 3105 | 298 |
Reaktionsdruck | 70 bar |
Reaktionstemperatur | 220 °C |
Reaktionszeit | 50 h |
LHSV (Isocamphylbrenzcatechin) | 0,5 ml/ml·h. |
Gas-Produkt-Volumenverhältnis H2 / Isocamphylbrenzcatechin | 4000:1 |
Katalysator | Katalysatorform Porenradien | Ausbeute an Sandelalkohol (%) | Ausbeute an Kohlenwasserstoffen (%) |
4 (erfind.) | Kugel 2,1 mm | 82,1 | 7,9 |
7 (Vergl.) | Tablette 3mm | 68,9 | 10,8 |
Reaktionsdruck | 20 bar |
Reaktionstemperatur | 80°C |
Reaktionszeit | 40 h |
LHSV | 0,5 ml/ml·h |
Gas-Produkt-Volumenverhältnis H2 / Feed | 250:1 |
Katalysator | Katalysatorform | Ausbeute an Methyl-Phenyl-Carbinol (%) |
5 (erfind.) | Kugel | 76,4 |
8 (Vergl.) | Trilobe-Extrudat | 66,9 |
Claims (15)
- Verfahren zur Herstellung geformter kugelförmiger Metall-Trägerkatalysatoren mit Metallgehalten von 10 bis 70 Masse-%, wobeiein in einem flüssigen Medium gelöstes oder suspendiertes Gemisch aus einem Polysaccharid und mindestens einer Metallverbindung, ausgewählt aus der Gruppe bestehend ausa) Metalloxiden,b) Metallhydroxiden,c) basischen Metallcarbonaten,d) Metallhydrogencarbonaten,e) Metallsilikaten,f) Metallzirkonaten,g) Metallaluminaten,h) Metalltitanaten,i) Metallchromiten undj) Metallalumnosilikatdie in der Metallsalzlösung erhaltenen Katalysatorkugeln nach einer Verweilzeit von 1 bis 180 Minuten aus dieser abgetrennt,bei Temperaturen von 80 bis 150°C getrocknet undbei Temperaturen von 150 bis 600°C reduziert werden.
- Verfahren nach Anspruch 1, wobei die Metallsalzlösung aus mindestens einem Metallion der mindestens einen ausgewählten Metallverbindung besteht.
- Verfahren nach Anspruch 1, wobei die Metallsalzlösung aus mindestens einem mehrwertigen Metallion ausgewählt aus der Gruppe bestehend aus Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Al3+ und Cr3+ besteht.
- Verfahren nach einem Ansprüche 1 bis 3, wobei die Metallionen-Konzentration 0,3 bis 5 Masse-%, vorzugsweise 1 bis 2 Masse-%, beträgt
- Verfahren nach einem Ansprüche 1 bis 4, wobei die Metallsalzlösung als Anionen Nitrat und/oder Acetat enthält.
- Verfahren nach einem der Ansprüche 1 bis 5, wobei dem Gemisch mindestens ein Zuschlagstoff zugefügt wird, der als Binder fungiert.
- Verfahren nach Anspruch 6, wobei der Zuschlagsstoff ausgewählt ist aus der Gruppe bestehend aus Tylose, Bentonit, Böhmit, Kaolin, Kieselgel, Kieselsol, Methylcellulose und Wasserglas.
- Verfahren nach Anspruch 6 oder 7, wobei das Feststoffverhältnis, bezogen auf den Glührückstand, der im Gemisch befindlichen mindestens einen Metallverbindung und dem mindestens einen Zuschlagstoff 4 bis 15 beträgt.
- Verfahren nach einem der vorangehenden Ansprüche, wobei das Feststoffverhältnis, bezogen auf den Glührückstand, der im Gemisch befindlichen mindestens einen Metallverbindung und dem mindestens einen Polysaccharid 4 bis 15 beträgt.
- Verfahren nach Anspruch 9, wobei als Polysaccharid Alginat eingesetzt wird.
- Verfahren nach einem der vorangehenden Ansprüche, wobei dem Gemisch ein oder mehrere Dotierungselemente von 0,1 bis 5 Masse-% zugesetzt werden.
- Verfahren nach Anspruch 11, wobei die Dotierungselemente Mg, Ca, Mn, Mo, Cr, Fe oder Zn sind.
- Verfahren nach einem der vorangehenden Ansprüche, wobei die erhaltenen Katalysatorkugeln nach der Trocknung und vor der Reduktion bei Temperaturen von 150 bis 600°C calciniert werden.
- Kugelförmiger Metall-Trägerkatalysator mit einem Metallgehalt von 10 bis 70 Masse-%, erhältlich durch ein Verfahren nach einem der Ansprüche 1 bis 13.
- Verfahren zur Hydrierung von Aromaten, wobei die Aromaten unter Einsatz eines kugelförmigen Metall-Trägerkatalysators mit einem Metallgehalt von 10 bis 70 Masse-%, erhältlich durch ein Verfahren nach einem der Ansprüche 1 bis 13, hydriert werden.
Applications Claiming Priority (2)
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DE10202127A DE10202127A1 (de) | 2002-01-22 | 2002-01-22 | Kugelförmige hochaktive Metall-Trägerkatalysatoren |
DE10202127 | 2002-01-22 |
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EP1331033A1 true EP1331033A1 (de) | 2003-07-30 |
EP1331033A8 EP1331033A8 (de) | 2004-07-28 |
EP1331033B1 EP1331033B1 (de) | 2007-03-14 |
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EP03001147A Expired - Lifetime EP1331033B1 (de) | 2002-01-22 | 2003-01-21 | Kugelförmige hochaktive Metall-Trägerkatalysatoren |
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US (2) | US7172990B2 (de) |
EP (1) | EP1331033B1 (de) |
JP (1) | JP4253193B2 (de) |
CN (1) | CN1313194C (de) |
AT (1) | ATE356663T1 (de) |
CA (1) | CA2416362A1 (de) |
DE (2) | DE10202127A1 (de) |
DK (1) | DK1331033T3 (de) |
ES (1) | ES2280631T3 (de) |
NO (1) | NO324701B1 (de) |
PL (1) | PL358053A1 (de) |
RU (1) | RU2317853C2 (de) |
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US8680350B2 (en) | 2006-07-17 | 2014-03-25 | Basf Se | Process for hydrogenating unsaturated hydrocarbons in the presence of catalysts containing copper and zinc |
WO2008104536A1 (de) * | 2007-02-27 | 2008-09-04 | Süd-Chemie AG | Reformierungskatalysator für schmelzcarbonatbrennstoffzellen |
EP2151426A1 (de) * | 2007-06-06 | 2010-02-10 | Ube Industries, Ltd. | Verfahren zur herstellung von 1,5-pentandiol und/oder 1,6-hexandiol |
EP2151426A4 (de) * | 2007-06-06 | 2011-09-14 | Ube Industries | Verfahren zur herstellung von 1,5-pentandiol und/oder 1,6-hexandiol |
WO2009050292A2 (en) * | 2007-10-19 | 2009-04-23 | Shell Internationale Research Maatschappij B.V. | Catalyst for the hydrogenation of unsaturated hydrocarbons and process for its preparation |
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EP2402299A1 (de) * | 2010-06-30 | 2012-01-04 | Shell Internationale Research Maatschappij B.V. | Verfahren zur Herstellung von Olefinen aus Synthesegas mit einem Kobalt und Mangan enthaltenden Katalysators |
CN110841648A (zh) * | 2019-11-19 | 2020-02-28 | 中国石油化工股份有限公司 | 用于n,n-二甲基-1,3-丙二胺的负载型催化剂及其制备和应用 |
Also Published As
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US20070117714A1 (en) | 2007-05-24 |
ES2280631T3 (es) | 2007-09-16 |
US7518023B2 (en) | 2009-04-14 |
DE50306779D1 (de) | 2007-04-26 |
PL358053A1 (en) | 2003-07-28 |
DE10202127A1 (de) | 2003-07-31 |
CN1433837A (zh) | 2003-08-06 |
CA2416362A1 (en) | 2003-07-22 |
RU2317853C2 (ru) | 2008-02-27 |
US7172990B2 (en) | 2007-02-06 |
NO20030181L (no) | 2003-07-23 |
CN1313194C (zh) | 2007-05-02 |
NO20030181D0 (no) | 2003-01-14 |
EP1331033B1 (de) | 2007-03-14 |
JP4253193B2 (ja) | 2009-04-08 |
EP1331033A8 (de) | 2004-07-28 |
JP2003260359A (ja) | 2003-09-16 |
NO324701B1 (no) | 2007-12-03 |
US20040220436A1 (en) | 2004-11-04 |
DK1331033T3 (da) | 2007-05-29 |
ATE356663T1 (de) | 2007-04-15 |
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